CN104250385A - Preparation method of polypropylene foaming sheet material - Google Patents
Preparation method of polypropylene foaming sheet material Download PDFInfo
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- CN104250385A CN104250385A CN201310270457.XA CN201310270457A CN104250385A CN 104250385 A CN104250385 A CN 104250385A CN 201310270457 A CN201310270457 A CN 201310270457A CN 104250385 A CN104250385 A CN 104250385A
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Abstract
The invention provides a preparation method of a polypropylene foaming sheet material. Homo-polypropylene as base resin and ammonium polyphosphate as a fire retardant undergo foaming in the presence of a supercutical fluid foaming agent so that the polypropylene foaming sheet material is prepared. The preparation method comprises that two or more stages of propylene homopolymerization reactions occur in two or more reactors connected in series, wherein external electron donors used in the two or more stages of reactions respectively are silane and diether compounds. The halogen-free flame-retardation polypropylene foaming sheet material obtained by the preparation method has the advantages of low production cost, short production period, compact foam apertures, uniform aperture distribution and high burning oxygen index and can be used in occasions of automobile parts, steamships and aircraft weight reduction assemblies, and electronic packaging and building decoration having high flame-retardation requirements.
Description
Technical field
The present invention relates to field of polymer technology, say further, relate to a kind of preparation method of halogen-free polypropylene flame redardant foaming plate.
Background technology
Micro-pore of polymer is made up of the thin bubble chamber film of minimum bubble and this bubble of parcel, and the volumetric ratio shared by gas is high, and thermal insulation, resiliency, floatability are good and cost performance is high, and therefore Application Areas is extensive.In recent years, polypropylene resin foam body is with its good performance and cost balance, and the feature such as can be recycled, be widely used in heat insualting building material, automobile component, the fields such as package buffer material.Such as, as constructional heat-insulating purposes, polypropylene resin foam sheet material is used for building floor or wall interiors, presents good heat-proof quality, commercially extensively gets the nod and use.
The method preparing polypropylene expanded body mainly comprises bead method and extrusion molding.The former utilizes and in pressurization closed container, uses the whipping agent such as carbonic acid gas or hydro carbons at high temperature under high pressure in the polypropylene GRANULES of impregnating dispersion in water, obtains expanded bead after under atmospheric pressure releasing rapidly, utilizes compression molding to obtain forming composition afterwards.But the method is for produce in batches, manufacturing process is numerous and diverse, and energy consumption is many, cannot continuous seepage, so there is the high feature of manufacturing cost.The latter drops into polypropene composition particle in an extruder, use carbonic acid gas as required, hydro carbons, chemical foaming agent or linking agent, under heating and pressurizing, carry out extrusion foaming after melting mixing, but the foaming plate percentage of open area using carbonic acid gas to obtain for whipping agent is high, and mechanical property is not good; The foaming plate expansion ratio using chemical foaming agent to obtain is low, and loss of weight is not obvious, and Application Areas is narrower.As described a kind of crosslinked polyolefin resin foam in Chinese patent CN200680017108.5, although this foam has good thermotolerance, this polypropylene foam can not be recycled be easy to cause environmental pollution because foaming process employs crosslinking coagent.Chinese patent CN200510057317.X describes a kind of method for producing polypropylene foamed sheet, but the method uses the chemical foaming agents such as AC whipping agent, and expansion ratio is lower, is not suitable for the foam material field high to loss of weight requirement.And utilize compression molding can prepare the foaming plate of certain size, eliminate the link of bead compression molding, in addition, effectively can reduce production energy consumption and cost, simplify production technique, enhance productivity, the sheet material that expansion ratio is larger can be produced.
It should be noted that the raw material polypropylene of foaming plate is easy to burning, particularly foaming product combustibility compared with non-foamed goods is higher, so have more inflammable feature.When polypropylene foamed plate is used for material of construction, automobile component and electrical apparatus product parts, need that there is flame retardant resistance or certainly flame-out property, therefore each research institution and industrial sector conduct extensive research it, to obtain the flame-retardant intumescent sheet material given and meet these and require.Chinese patent 02824180.0 describes a kind of flame-retardant polyolefin resin pre-expanded beads, is made up of the polyolefins composition of polyolefin resin and sterically hindered amines ethers fire retardant.But this expanded particle needs just can obtain corresponding expanded molded article or sheet material by molded.
In recent years, expansion type flame retardant becomes the principal item of Flame Retardant Agent of Polypropylene, and this fire retardant is a kind of fire retardant of phosphorus nitrogen synergistic, and not halogen-containing.Polypropylene material containing this based flame retardant is when being heated, and it is bulk and have the foam layer of charcoal of enclosed construction that surface energy generates one deck, and this foam layer of charcoal has quadruple effect of fire-retardant, oxygen barrier, smoke elimination and anti-drippage, is a kind of rising fire retardant.Chinese patent 201210298715.0 describes a kind of manufacture method of halogen-free polypropylene flame redardant foam, and this foam uses Halogen phosphorus flame retardant, but foaming process needs cross-linking radiation, causes product to recycle equally.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of flame-retardant expanded preparation of plates method of high melt strength, propylene under supercritical state.Obtain meet environmental requirement degradable, uniform foam cell, rate of closed hole is high, physical heat resistance is high, density is controlled, mechanical property is good, production cost is low and the polypropylene foamed plate of applicable large-scale production.
The invention provides a kind of preparation method of polypropylene foamed plate, described foaming plate adopts homo-polypropylene to be matrix resin, take ammonium polyphosphate as fire retardant, exists issue brewed obtaining at supercritical fluid aerating powder; Wherein, described homo-polypropylene is adopted and is prepared with the following method: in the reactor of two or more serial operation, carry out two benches or more propylene homo and close reaction, wherein, under the Ziegler-Natta catalyst comprising the first external electron donor component exists, carry out first stage propylene homo close reaction, the MFR of resulting polymers controls to be 0.01 ~ 0.4g/10min; Subordinate phase propylene homo conjunction reaction is proceeded on the basis of first stage resultant of reaction, under hydrogen and the second external electron donor component exist; Merge two sections of resulting polymers and obtain described homo-polypropylene, it is 0.2 ~ 15g/10min that its MFR controls; And wherein said first external electron donor is silane compound, the second external electron donor is diether compound.
In above-mentioned preparation method, preferably, described silane compound is four and connects organic group on the silicon atoms optionally from the compound of alkyl and alkoxyl group.More preferably, described silane compound is for being selected from tetramethoxy-silicane, n-propyl triethoxyl silane, isobutyl triethoxy silane, trimethoxysilane, vinyltrimethoxy silane, n-propyl Trimethoxy silane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, Cyclohexylmethyldimethoxysilane, methyl-isobutyl dimethoxysilane, Dicyclohexyldimethoxysilane, one or more in phenyltrimethoxysila,e and dicyclopentyl dimethoxyl silane.
In the present invention, preferably, described diether compound is 1,3-diether compound, and its general structure is:
Wherein, R
1and R
2identical or different, preferred R
1and R
2be the straight chained alkyl of C1 ~ C20; R
3~ R
8mutually the same or different, be selected from the one in hydrogen, halogen atom, C1 ~ C20 alkyl of straight or branched, C3 ~ C20 cycloalkyl, C6 ~ C20 aryl, C7 ~ C20 alkaryl, C7 ~ C20 aralkyl, R
3~ R
8group between can be linked to be ring by key.
More preferably, described diether compound is for being selected from 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal, 2, 2-phenyl-1, 3-Propanal dimethyl acetal, 2, 2-phenmethyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-3, 7-dimethyl octyl-Propanal dimethyl acetal, 2, 2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl methyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-di ethyl propyl ether, 2, 2-diisobutyl-1, 3-dipropoxy propane, 2-sec.-propyl-2-isopentyl-1, 3-di ethyl propyl ether, 2-sec.-propyl-2-isopentyl-1, 3-dipropoxy propane and 2, two (cyclohexyl methyl)-1 of 2-, one or more in 3-di ethyl propyl ether.
In the present invention, preferably described Ziegler-Natta catalyst comprises following component, a kind of be main ingredient with magnesium, titanium, halogen and internal electron donor ingredient of solid catalyst A, a kind of organoaluminum B component and the first external electron donor component C, part by weight wherein between component A and B component counts 1:10 ~ 500 with titanium aluminum ratio, and the part by weight between B component and component C is 10 ~ 150:1.In a specific examples of aforesaid method, the mol ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and 1,3-diether compound external electron donor is 1:1 ~ 30:1, is preferably 2:1 ~ 15:1.
In the preparation process of matrix resin homo-polypropylene of the present invention, the added hydrogen of first stage and subordinate phase controls with the requirement of final MFR.Preferably, in the first phase, hydrogen content is less than or equal to 400ppmV; And hydrogen content is higher than hydrogen content in the first stage in subordinate phase.
In the above-mentioned methods, the described first stage is all polymerized and in Liquid-liquid, or can carries out in gas phase-gas phase, or adopts liquid-gas combination technique to carry out.In a specific embodiment, its polymerization methods is liquid-phase bulk polymerization.When carrying out liquid polymerization, polymerization temperature is 50 ~ 100 DEG C, with 60 ~ 85 DEG C as well; Polymerization pressure should higher than the saturated vapour pressure of propylene under corresponding polymerization temperature.When vapour phase polymerization, polymerization temperature is 50 ~ 100 DEG C, with 60 ~ 85 DEG C as well; Polymerization pressure can be normal pressure or higher, and preferred pressure is 1.0 ~ 3.0MPa(gauge pressure, lower same).The equal polyreaction of described subordinate phase is carried out usually in the gas phase, and polymerization temperature is 50 ~ 100 DEG C, with 60 ~ 85 DEG C as well; Polymerization pressure can be normal pressure or higher, and preferred pressure is 1.0 ~ 3.0MPa(gauge pressure, lower same).Above-mentioned equal polyreaction can be carried out continuously, also may be carried out batchwise.Successive polymerization can be Liquid-phase reactor and/or the Gas-phase reactor of two or more series connection, Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor or vertical mixing bed bioreactor or fluidized-bed reactor etc., and above Liquid-phase reactor and Gas-phase reactor also can at random matched combined.
In the above-mentioned methods, the described catalyzer comprising silicane external electron donor can directly join in the first reactor, after the pre-contact (pre-mixing) also can known altogether through industry and/or prepolymerization, then joins in the first reactor.Described prepolymerization refers to that catalyzer carries out the prepolymerization of certain multiplying power at a lower temperature, to obtain desirable particle shape and dynamic behavior control.It can be the continuous prepolymerization of liquid-phase bulk, can also be batch pre-polymerization in the presence of an inert solvent.Prepolymerization temperature is generally-10 ~ 50 DEG C, is preferably 5 ~ 30 DEG C.Before prepolymerization technology, optionally pre-contacting steps is set; Described pre-contacting steps refers to that promotor in catalyst system, external electron donor and Primary Catalysts (solid active center component) carry out the complex reaction of catalyst system, to obtain the catalyst system with polymerization activity.The temperature of pre-contacting steps controls as-10 ~ 50 DEG C usually, is preferably 5 ~ 30 DEG C.In the present invention, preferably before first stage propylene homo closes, described first external electron donor participates in For Propylene Pre-polymerization; Preferably before subordinate phase propylene homo closes, described second external electron donor participates in pre-mixing.
In the present invention, preferably, be also included in the preparation method of polypropylene foamed plate that to add silicon rubber be synergistic fire retardant.Synergistic fire retardant is added in the expanding fire retardant of expanded flame-retardant polypropylene system, flame retarding efficiency can be significantly improved, and reduce the add-on of expanding fire retardant in fire retardant systems, obtain the foaming plate goods of mechanics and processability improvement, the flame-retardancy requirements of military and civilian polypropylene foamed plate can be met.
In a kind of embodiment of the present invention, the preparation method of described foaming plate is: after comprising matrix resin, Nucleating Agent, main flame retardant ammonium polyphosphate and optional synergistic fire retardant, additive melt blending, be shaped to polypropylene board to be foamed, then moulded from foam is described polypropylene foamed plate in supercritical fluid aerating powder environment.
This Nucleating Agent can be a kind of inorganic powder as zinc borate, silicon-dioxide, talcum, calcium carbonate, borax or aluminium hydroxide, wherein preferred boric acid zinc or silicon-dioxide, according to fire-retardant composite effect, more preferably zinc borate; When matrix resin high melt strength, propylene is 100 weight part, described Nucleating Agent is 0.001 ~ 1 weight part, is preferably 0.01 ~ 0.05 weight part.In combustion, as the Nucleating Agents such as zinc borate can also form vitreum by the gap closing between block charcoal, be expected the barriering effect improving barrier layer.
Ammonium polyphosphate is as the main flame retardant in expansion type flame retardant, and it can be commercially available high polymerization degree APP, and its polymerization degree is greater than 1000, P
2o
5content is greater than 70%, and density is 1.9g/cm
3, decomposition temperature is greater than 270 DEG C, and solubleness is less than 0.1g/100ml H
2o(25 DEG C), for the matrix resin of every 100 weight parts, the usage quantity of this fire retardant is 1 ~ 80 weight part, preferably 10 ~ 35 weight parts.
Silicon rubber adds system as a kind of synergistic fire retardant, silicon rubber is by commercially available acquisition, or prepare fully sulfurized silicon rubber powder (VP-601) according to Chinese patent ZL01801656.1, its median size≤2 μm, preferably between 0.1 ~ 0.5 μm, described fully sulfurized silicon rubber powder particle is preferably equal phase structure.For every this matrix resin of 100 weight parts, the usage quantity of this additive is 0 ~ 0.1 weight part, preferably 0.001 ~ 0.005 weight part.Adding of silicon rubber can improve material at high temperature thermostability, and improves material carbon yield.Adding of a small amount of silica gel makes material combustion Char Residues Structure finer and close, effectively can suppress the further burning of polymkeric substance.
In the present invention, described additive is one or more in oxidation inhibitor, uv-absorbing agent, antistatic agent, fire retardant, metal inactivator, pigment, nucleating agent, Foam Control, filler, stablizer, toughener and lubricant.
The present invention also provides any one method above-mentioned the corresponding polypropylene foamed plate prepared.
The inventive method is the method for the polypropylene microporous foam material of the excellent performance that a kind of High-efficient Production aperture is less, hole density is higher.The halogen-free polypropylene flame redardant foaming plate utilizing present method to prepare, have cost low, become the product cycle short, abscess is fine and close and even aperture distribution, burns oxygen index advantages of higher, can be applicable to trolley part, steamer and aircraft loss of weight assembly and electronic packaging and building decoration etc. have the occasion compared with high flame retardant requirement to foam plastic product.
Accompanying drawing explanation
Fig. 1 is the foaming plate cross section electromicroscopic photograph of embodiment 4;
Fig. 2 is the foaming plate cross section height multiple electromicroscopic photograph of embodiment 4.
Embodiment
Melt flow rate (MFR) (MFR): by ISO1133, adopts CEAST company 7026 type Melt Flow Rate Measurer, at 230 DEG C, measures under 2.16kg load.Moulded from foam machine: M90, Nanjing Han Yi Mechanical Equipment Company.Melt drawn test machine: Rheotens
tM97, German Goettfert company.
Density tester: CPA225D, density annex YDK01, German Satorius company.Testing method: the density annex using Satorius balance, utilizes drainage to obtain the density of polypropylene matrix resin and polypropylene foamed plate.The expansion ratio formula b=ρ of the polypropylene foamed plate obtained
1/ ρ
2calculate, wherein, b is expansion ratio, ρ
1for the density of polypropylene matrix resin, ρ
2for the density of polypropylene foam material; Density in the present invention all refers to the apparent density of material.
Oxygen index: the method described by GB GB2406-2 measures.
The following example further describes the present invention, but should illustrate, the present invention is in no way limited to these embodiments.
The preparation of matrix resin HMSPP501
Polyreaction is carried out on a set of polypropylene pilot plant.Its major equipment comprises prepolymerization reactor, first ring pipe reactor and the second annular-pipe reactor.
Prepolymerization: flow is Primary Catalysts (the DQ-III catalyzer of about 0.5g/hr, China Petrochemical Industry's catalyst Co. Beijing Ao Da branch office provides), flow is the promotor (triethyl aluminum) of 6.33g/hr, flow is the first external electron donor (dicyclopentyl dimethoxyl silane of 0.63g/hr, DCPMS) through 6 DEG C, after 20min pre-contact, add continuously stirring autoclave prepolymerization reactor continuously and carry out prepolymerization, prepolymerization is carried out under propylene liquid-phase bulk environment, temperature is 15 DEG C, the residence time is about 4min, under this condition, the pre-polymerization multiple of catalyzer is about 120 ~ 150 times.The TEA/DCPMS mol ratio entering prepolymerization reactor is 20.
Propylene homo in annular-pipe reactor closes: pre-polymerization rear catalyst enters continuously in first ring pipe reactor and completes first stage propylene homo conjunction reaction, loop po lymerisation temperature of reaction 70 DEG C, reaction pressure 4.0MPa, not hydrogenation in the charging of annular-pipe reactor, the density of hydrogen ﹤ 10ppmV that on-line chromatograph detects, obtains propene polymer.Add second external electron donor 2, the 2-diisobutyl-1,3-Propanal dimethyl acetal (DIBMP) of 0.59g/hr in the polymer slurries exit of the first reactor, make the propene polymer pre-mixing that itself and first stage obtain; Wherein TEA/DIBMP mol ratio is 20.Material after pre-mixing is entered the second reactor, in the second reactor, adds a certain amount of hydrogen, it is 4000ppmV that on-line chromatograph detects density of hydrogen, continues to cause propylene homo and close reaction in the second reactor.After having reacted, remove the activity of catalyst in reactor through wet nitrogen, merge the polymkeric substance of two benches generation and through heat drying, obtain described homo-polypropylene.
The preparation of matrix resin HMSPP502
With the preparation of matrix resin HMSPP501, but add a small amount of hydrogen in first ring pipe reactor, it is 300ppmV that on-line chromatograph detects density of hydrogen, and changes the density of hydrogen in the second annular-pipe reactor into 5000ppmV; In addition, adjustment makes TEA and DCPMS mol ratio in first ring pipe reactor be that in the 10, second annular-pipe reactor, TEA and DIBMP mol ratio is adjusted to 60.
Table 1 lists the analytical results of two kinds of matrix resin HMSPP501 and HMSPP502 and common homo-polypropylene T30S of the prior art.
Table 1
In the preparation process of matrix resin homo-polypropylene in the present invention, be according to the requirement to different molecular weight fraction, in different reactor, add the external electron donor with different qualities.Particularly, in first stage i.e. the first reactor, the present invention needs the propene polymer preparing high molecular weight block, in order to make this fraction have higher molecular weight, have selected a kind of external electron donor with lower hydrogen response, i.e. silane compound; And in subordinate phase, the present invention needs the propene polymer preparing lower molecular weight fraction, in order to the hydrogen of less amount can be used, have selected the external electron donor that a kind of higher hydrogen adjusts susceptibility, i.e. diether compound.
In addition, the two ethers external electron donors added in the present invention are compared with the silicane external electron donor in prior art (WO2011/088754), have stronger with ability that is catalyst active center's complexing, it can react with the catalytic active center in first stage resulting polymers particle, generate new catalytic active center, continue all polymerizations causing propylene.
Polymerization process of the present invention not only can obtain the propene polymer compared with wide molecular weight, and its maximum feature is that the content of ultra high molecular weight fraction (molecular weight is greater than 5,000,000) is higher, simultaneously the content of lower molecular weight fraction (molecular weight is less than 50,000) also can ensure to be greater than a certain amount of, make the melt strength of gained propene polymer have like this to improve significantly, but also ensure that the processing characteristics of polymkeric substance.
The preparation of foaming plate
Prepare flame retardation modification polypropylene compound resin: in the present invention, can wire rod be become via one or more extrusion of twin screw or single screw extruder and cut, obtain acrylic resin particle.This process is passed through matrix resin, fire retardant, synergistic fire retardant, Nucleating Agent, after additive utilizes homogenizer blended, extrudes also pelletizing obtain flame-retardant modified particle by twin screw extruder.
Overcritical moulded from foam: heated up by the foaming mould on moulding press, after blowing temperature to be achieved, puts into matched moulds after mould by fire-retardant particle; Until all particles reach can there is viscoelastic deformation temperature range in after, in mould, be filled with supercritical carbon dioxide fluid, this supercritical fluid pressures is 3 ~ 35MPa, supercutical fluid swelling diffusion 5 ~ 120 minutes in polypropylene; Moulding press die sinking pressure release foaming within 1 ~ 10 second time subsequently, can obtain abscess-size and the controlled polypropylene foam material of density.
Described moulding press can install one deck or multilayer foamed mould; Described foaming mould is the high pressure resistant mould of copper alloy, aluminium alloy or stainless steel, containing top plate and lower bolster; Described blowing temperature is that polypropylene can occur in the temperature range of viscoelastic state deformation, and for semi-crystalline polymer polypropylene, blowing temperature is lower than its fusing point 0.05 ~ 50 DEG C, and preferably, blowing temperature is 50 ~ 120 DEG C.Described supercutical fluid is such as the mixed gas of supercritical co, supercritical nitrogen or their arbitrary ratio; Be 100 parts of calculating with polypropylene weight, after reaching diffusive equilibrium, the supercritical flow body burden be dissolved in polypropylene is 0.1 ~ 30 part; Described pressure releasing die sinking can for first to let out to the arbitrary pressure lower than saturation pressure by pressure release valve by the supercritical fluid pressures in mould, then die sinking; Or direct die sinking under supercritical fluid conditions; The volume expansion ratio of the microcellular foam material obtained under above-mentioned condition is 2 ~ 60 times, and mean pore size is 0.1 ~ 100 μm, and hole density is 1 × 10
6~ 1 × 10
15individual/cm
2.
The present invention realizes microporous foam by importing supercutical fluid in mould pressing die.Oil hydraulic system due to moulding press can realize the sealing of mould, and the temperature control system of moulding press can realize the control to die temperature, therefore can realize supercutical fluid atmosphere in mould, provide polypropylene expanded environment.Thus polypropylene can be made to be in the supercritical fluid environment of High Temperature High Pressure by the mould of moulding press, and reach supercutical fluid to the dissolving diffusive equilibrium in polypropylene matrix, then by reducing pressure, causing the coring and increment of abscess in polypropylene matrix, obtaining microcellular foam material.
Embodiment 1 ~ 7
The homo-polypropylene HMSPP501 of 100 weight parts or HMSPP502, Cell-controlling agents (zinc borate), main flame retardant (ammonium polyphosphate) and synergistic fire retardant (silicon rubber) and additive are put into homogenizer high speed and mixes 30 seconds, after to add German Ke Beilong company ZSK-25 type twin screw extruder mixing, moment of torsion controls about 65%, rotating speed 300rpm.Embodiment 1 ~ 6 additive used includes the antioxidant 1010 (BASF AG) of 0.2 weight part and the irgasfos 168 (BASF AG) of 0.1 weight part.Use HMSPP501 for matrix resin in embodiment 1 ~ 4 and 7, and embodiment 5 and 6 use HMSPP502 to be matrix resin.
By the molten state modified resin that obtains after mixing by mouth mold forming, cooling is blocked, and makes the polypropylene board to be foamed of 20 × 20 × 1cm.The mould be arranged between moulding press is warming up to certain temperature, matrix resin homo-polypropylene is put into wherein, moulding press matched moulds, die sealing.In mould, pass into the supercritical carbon dioxide gas of certain pressure, make it under this temperature, pressure, diffuse into polypropylene matrix.After saturated 30min, reach diffusive equilibrium, by pressure release valve by the Pressure Drop in mould to certain pressure, then die sinking pressure release foaming, flame-retardant expanded sheet material ejects, and cools qualitative, obtains polypropylene fire retardant microporous foam sheet material.In table 2, foamed board density adopts GB/T6343-2009 to measure.
Comparative example 1 ~ 4
The common homo-polypropylene T30S adopting Sinopec Qilu Branch Company to produce replaces HMSPP501 and HMSPP502 in embodiment to test.
Utilize molding forming machine that the foaming plate prepared in above-described embodiment and comparative example is processed into batten according to the specification of 1 × 1 × 15cm, and carry out oxygen index test according to the method that GB GB T2406.2-2009 describes, it the results are shown in Table 2.
Table 2
From experimental result, be the high melt strength, propylene of HMSPP501 or HMSPP502 with the trade mark in embodiment 1 ~ 7 be matrix resin, obtain the foaming plate with bimodal cell structure, abscess dense uniform.More preferably, by adding the synergistic fire retardant silicon rubber of trace, after itself and Nucleating Agent interact, effectively can reduce the addition of main flame retardant ammonium polyphosphate, can produce when main flame retardant ammonium polyphosphate addition is 15 ~ 25 parts oxygen index higher than 30 flame retardant products.Can find out that fire-retardant particles is evenly distributed from the cross section electromicroscopic photograph shown in embodiment 4 corresponding figures 2.And the panel density using common homo-polypropylene T30S to obtain in comparative example 1 ~ 4 is larger, cell density is low and uneven, even if add a large amount of main flame retardant and synergistic fire retardant still cannot meet oxygen index requirement, mainly because the lower part abscess that causes of melt strength of T30S merges, effectively cannot form flame-retardant layer.
Claims (10)
1. a preparation method for polypropylene foamed plate, is characterized in that, described foaming plate adopts homo-polypropylene to be matrix resin, take ammonium polyphosphate as fire retardant, exists issue brewed obtaining at supercritical fluid aerating powder; Wherein, described homo-polypropylene is adopted and is prepared with the following method: in the reactor of two or more serial operation, carry out two benches or more propylene homo and close reaction, wherein, under the Ziegler-Natta catalyst comprising the first external electron donor component exists, carry out first stage propylene homo close reaction, the MFR of resulting polymers controls to be 0.01 ~ 0.4g/10min; Subordinate phase propylene homo conjunction reaction is proceeded on the basis of first stage resultant of reaction, under hydrogen and the second external electron donor component exist; Merge two sections of resulting polymers and obtain described homo-polypropylene, it is 0.2 ~ 15g/10min that its MFR controls; And wherein said first external electron donor is silane compound, the second external electron donor is diether compound.
2. method according to claim 1, is characterized in that, described silane compound is four and connects organic group on the silicon atoms optionally from the compound of alkyl and alkoxyl group, preferred described silane compound is for being selected from tetramethoxy-silicane, n-propyl triethoxyl silane, isobutyl triethoxy silane, trimethoxysilane, vinyltrimethoxy silane, n-propyl Trimethoxy silane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, Cyclohexylmethyldimethoxysilane, methyl-isobutyl dimethoxysilane, Dicyclohexyldimethoxysilane, one or more in phenyltrimethoxysila,e and dicyclopentyl dimethoxyl silane.
3. method according to claim 1, is characterized in that, described diether compound is 1,3-diether compound, and its general structure is:
Wherein, R
1and R
2identical or different, preferred R
1and R
2be the straight chained alkyl of C1 ~ C20; R
3~ R
8mutually the same or different, be selected from the one in hydrogen, halogen atom, C1 ~ C20 alkyl of straight or branched, C3 ~ C20 cycloalkyl, C6 ~ C20 aryl, C7 ~ C20 alkaryl, C7 ~ C20 aralkyl, R
3~ R
8group between can be linked to be ring by key.
4. method according to claim 3, it is characterized in that, described diether compound is for being selected from 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal, 2, 2-phenyl-1, 3-Propanal dimethyl acetal, 2, 2-phenmethyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-3, 7-dimethyl octyl-Propanal dimethyl acetal, 2, 2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl methyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-di ethyl propyl ether, 2, 2-diisobutyl-1, 3-dipropoxy propane, 2-sec.-propyl-2-isopentyl-1, 3-di ethyl propyl ether, 2-sec.-propyl-2-isopentyl-1, 3-dipropoxy propane and 2, two (cyclohexyl methyl)-1 of 2-, one or more in 3-di ethyl propyl ether.
5. according to the method in Claims 1 to 4 described in any one, it is characterized in that, before first stage propylene homo closes, described first external electron donor participates in For Propylene Pre-polymerization; And/or described second external electron donor participates in pre-mixing before subordinate phase propylene homo closes.
6. according to the method in Claims 1 to 4 described in any one, it is characterized in that, be also included in the preparation method of polypropylene foamed plate that to add silicon rubber be synergistic fire retardant.
7. method according to claim 1, is characterized in that, described whipping agent is carbonic acid gas and/or nitrogen.
8. according to the method in claim 1 ~ 7 described in any one, it is characterized in that, after comprising matrix resin, Nucleating Agent, main flame retardant ammonium polyphosphate and optional synergistic fire retardant, additive melt blending, be shaped to polypropylene board to be foamed, then moulded from foam is described polypropylene foamed plate in supercritical fluid aerating powder environment.
9. method according to claim 8, is characterized in that, described Nucleating Agent be selected from zinc borate, silicon-dioxide, talcum, calcium carbonate, borax and aluminium hydroxide one or more; When matrix resin is 100 weight part, described Nucleating Agent is 0.001 ~ 1 weight part, is preferably 0.01 ~ 0.05 weight part, described main flame retardant is 1 ~ 80 weight part, is preferably 10 ~ 35 weight parts, and described synergistic fire retardant is 0 ~ 0.1 weight part, is preferably 0.001 ~ 0.005 weight part.
10. the polypropylene foamed plate prepared as method as described in any one in claim 1 ~ 9.
Priority Applications (1)
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Cited By (6)
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| CN108045050A (en) * | 2017-11-22 | 2018-05-18 | 杭州捷尔思阻燃化工有限公司 | A kind of low VOC foam sandwiches high-strength light halogen-free flame-retardant composite material and preparation method thereof |
| CN108250577A (en) * | 2018-01-17 | 2018-07-06 | 杭州汉克斯隔音技术工程有限公司 | A kind of expanded polypropylene beads and its preparation process of fire-retardant low heat conduction |
| CN109366839A (en) * | 2018-09-21 | 2019-02-22 | 四川大学 | The method that molding physical blowing prepares hole-closing structure rubbery foam |
| CN111675821A (en) * | 2020-06-09 | 2020-09-18 | 浙江新恒泰新材料有限公司 | Preparation method of low-shrinkage high-magnification long-acting antibacterial polyurethane foam board |
| CN114085455A (en) * | 2021-11-20 | 2022-02-25 | 南京聚隆科技股份有限公司 | Low-density flame-retardant polypropylene foam material and preparation method thereof |
| CN114083740A (en) * | 2021-11-19 | 2022-02-25 | 苏州申赛新材料有限公司 | Method for preparing bicolor foamed sheet based on space limitation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108045050A (en) * | 2017-11-22 | 2018-05-18 | 杭州捷尔思阻燃化工有限公司 | A kind of low VOC foam sandwiches high-strength light halogen-free flame-retardant composite material and preparation method thereof |
| CN108250577A (en) * | 2018-01-17 | 2018-07-06 | 杭州汉克斯隔音技术工程有限公司 | A kind of expanded polypropylene beads and its preparation process of fire-retardant low heat conduction |
| CN109366839A (en) * | 2018-09-21 | 2019-02-22 | 四川大学 | The method that molding physical blowing prepares hole-closing structure rubbery foam |
| CN109366839B (en) * | 2018-09-21 | 2020-12-22 | 四川大学 | Method for preparing closed-cell structure rubber foam material by mould pressing physical foaming |
| CN111675821A (en) * | 2020-06-09 | 2020-09-18 | 浙江新恒泰新材料有限公司 | Preparation method of low-shrinkage high-magnification long-acting antibacterial polyurethane foam board |
| CN114083740A (en) * | 2021-11-19 | 2022-02-25 | 苏州申赛新材料有限公司 | Method for preparing bicolor foamed sheet based on space limitation |
| CN114083740B (en) * | 2021-11-19 | 2024-04-30 | 苏州申赛新材料有限公司 | Method for preparing double-color foaming sheet material based on space limitation |
| CN114085455A (en) * | 2021-11-20 | 2022-02-25 | 南京聚隆科技股份有限公司 | Low-density flame-retardant polypropylene foam material and preparation method thereof |
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